Hydrocarbon conversion catalyst

ABSTRACT

The conversion of hydrocarbons in the presence of hydrogen occurs under hydrocarbon conversion conditions in the presence of a subgroup of a certain class of metal-substituted semi-crystalline aluminosilicates which are synthetic and which are predominantly ordered in two directions, that is, which are laminar or have a layered or stacked sheet structure. The metal substituted for the aluminum in the trioctahedral sites is nickel, cobalt, or mixtures thereof. Hydrocarbon conversion catalysts are also claimed comprising the metal-substituted laminar 2:1 layer lattice aluminosilicate minerals containing in addition a hydrogenation component such as palladium. The catalysts are preferably used in hydroisomerization and hydrocracking processes.

This is a continuation-in-part application of U.S. Ser. No. 441,059filed Feb. 11, 1974 "abandoned", which is in turn a continuation-in-partapplication of U.S. Ser. No. 291,263 filed Sept. 22, 1972 "abandoned",both applications being assigned to the same assignee as the presentapplication.

This invention relates to a hydrocarbon conversion process and to acatalyst therefor. More particularly, this invention relates to aprocess for the conversion of hydrocarbons in the presence of hydrogenusing certain metal-substituted synthetic aluminosilicate minerals ascatalysts.

The conversion of hydrocarbons in the presence of hydrogen to produceproducts of upgraded value is of special interest to the petroleumindustry. Such processes represent, for example, the hydrocracking offurnace oils to produce high octane number gasoline, the hydrogenationof residuals to remove sulfur, the hydroisomerization of hydrocarbonssuch as straight-chain hydrocarbons to produce branched chain structureswhich are of higher octane number as gasoline components; thehydrocracking of raffinate hydrocarbons to form liquid petroleum gas;etc. It is particularly important that these reactions be performedefficiently, that is, with as little undesirable side reactions aspossible. For example, in the hydrocracking of furnace oils to obtainhigh octane number gasoline, it is desirable to retain aromatics whilereducing the boiling point of the charge stock into the gasoline range.It is also desirable to perform this hydrocracking operation at as low atemperature and pressure as possible. Many catalysts have been proposedin the prior art to perform the above type of hydrocarbon conversionreactions in the presence of hydrogen, but the prior art catalysts havecertain undesirable characteristics associated with them, such as pooractivity at low temperatures or the indiscriminate hydrocracking ofaromatics when it is desirable that such aromatics be retained.

It has now been discovered in accordance with the invention that asubgroup of a certain class of metal-substituted semi-crystallinealuminosilicates which are synthetic and which are predominantly orderedin two directions, that is, which are laminar or have a layered orstacked sheet structure, are highly active and selective hydrocarbonconversion catalysts. In accordance with the invention, a hydrocarbontype charge stock is reacted in the presence of hydrogen and in thecontact presence of a catalyst comprising:

A LAMINAR 2:1 LAYER-LATTICE ALUMINOSILICATE MINERAL POSSESSINGLAYER-LATTICE UNIT CELLS, EACH CELL HAVING AN INHERENT NEGATIVE CHARGEBALANCED BY CATIONS EXTERIOR TO SAID UNIT CELL, SAID MINERALCORRESPONDING TO THE FOLLOWING OVERALL FORMULA PRIOR TO DRYING ANDCALCINING:

    [(Al.sub.4.sup.+ew.sup.3.sub.- Y.sub.3w.sup.2.sub.-).sup.VI (Q.sub.8.sup.+x.sup.4.sub.- Al.sub.x.sup.3.sub.-).sup.IV O.sub.20 (OH).sub.4.sup.+f F.sub.f ].sup.. [dC.sup.y ]

where Al is aluminum;

Y is selected from the class consisting of nickel, cobalt and mixturesthereof;

Q is at least 0.95 mol fraction silicon ions, the remainder consistingof tetravalent ions having an ionic radius not to exceed 0.65 A;

F is fluorine;

C is at least one charge-balancing cation; and

where e has a numerical value from 2 to 3 inclusive;

w has a numerical value from 0.01 to 2 inclusive, with the proviso thatthe quantity ew have a numerical value from 0.02 to 4 inclusive;

f has a value of 4 or less;

x has a numerical value from 0.05 to 2.0 inclusive;

y is the valence of the cation C; and

d is the number of cations C where the product dy = x + 3(e-2)w.

In the above formulation, the first bracket represents the overallaverage laminar layer-lattice unit cell structure formulation, which, aswill be explained hereinbelow, possesses an inherent negative charge byreason of the fact that the positive charges of the cations are lessthan the negative charges of the anions. Since the preparation as awhole is electrostatically neutral, the charge-balancing cations whichare necessarily present are external to the lattice and are representedby the second bracket, in which C stands for the charge-balancingcations taken as a whole, with y being their average charge and d beingthe number of charge-balancing cations per unit cell. It will berecognized that in this formulation, C may actually correspond to alarge variety of charge-balancing cations simultaneously present, suchas, for example, a mixture of hydrogen, calcium and the like cations.For catalytic purposes, it is preferred that the mineral be free ofalkali metals which can occur in the exchange sites (C) due to thepresence of alkali metals, for example, in the preparative solutions.Minor amounts of alkali metals, such as 5 to 10% of the exchange sites,or as much as 35% of the exchange sites, can be tolerated.

It is clear from the formulation given that Y consists of divalentnickel or cobalt ions either isomorphously substituted for a like numberof aluminum ions, whereby a charge deficit results, or substituted onthe basis of three divalent ions for two aluminum trivalent ions with noresulting charge deficit, or a mixture of both. In like manner, it isclear that Q, while consisting predominantly of silicon ions, mayinclude a minor proportion of tetravalent ions isomorphously substitutedfor some of the silicon ions without affecting the overall charge; whiletrivalent aluminum ions in proportion represented by subscript xisomorphously substituted for a like number of silicon ions, whereby acharge deficit results from the substitution of a trivalent ion for atetravalent ion.

For the sake of convenience, a tabulation follows in which the Y and Qelements usable in accordance with the invention are listed. It will beclear that this listing results from checking each element against itsknown valence states and its known ionic radius for each applicablevalence state, taking into account the coordination number where thelatter affects the ionic radius. Tables of ionic radii for variouselements have appeared in the literature during the last half century,and in the case of disparity among the values given for a specifiedelement, the best value has been chosen in the light of all of the knowndata, and this best value is the one which appears in the tables whichfollow.

                  TABLE A                                                         ______________________________________                                        Y: Divalent -- Maximum 0.75 A                                                 ______________________________________                                        Nickel          (Ni)        0.69                                              Cobalt          (Co)        0.72                                              ______________________________________                                    

                  TABLE B                                                         ______________________________________                                        Q: Tetravalent -- Maximum 0.65 A                                              ______________________________________                                        Silicon         (Si)        0.41                                              Germanium       (Ge)        0.53                                              ______________________________________                                    

Preferably, in the above unit cell formula, Q is silicon. Further, thevalue of e is preferably about 2; the value of w from 0.2 to 1.66 withthe value of ew being preferably from 0.4 to 3.32. The value of x ispreferably from 0.5 to 2, and the value of f is preferably from 0.5 to3.75.

Moreover, usually, although not necessarily, the composition of thecharge-balancing cations in the second bracket contains some proportionof the partial hydroxides of aluminum. Thus, in accordance with a moreparticular formulation, the composition of the charge-balancing cationsin the second bracket contains some proportion of the partial hydroxidesof aluminum. Thus, in accordance with a more particular formulation, thecomposition of the charge-balancing cations in the second bracket mayconveniently be represented as follows:

    [a M.sup.n + b Al (OH).sub.3.sub.-z.sup.z ]

wherein

    an + bz = dy = x + 3(e-2)w

and M is at least one charge-balancing cation and is preferably selectedfrom the group consisting of hydrogen; ammonium; substituted ammonium;substituted phosphonium; multivalent metal cations other than aluminum;and partial hydroxides of multivalent metal cations; and n is theunsatisfied valence of M. In practice, the product bz is a small valuecompared to the product an.

This second, more particular characterization of the charge-balancingcations is believed to correspond more closely to the products initiallyobtained in accordance with the preferred mode of preparation. Moreover,it provides explicitly for any hydroxyaluminum cations which may bepresent. It will be understood that such hydroxyaluminum cations arecommonly present as a mixture of species, as described, for example, inU.S. Geological Survey Water-Supply Paper 1827-A (1967), which isincorporated herein by reference. However, since these charge-balancingcations are essentially exchangeable without disturbing the latticeitself, the latter being represented by the first bracket, after havingmade a given preparation in accordance with the invention by a preferredprocedure, it is relatively simple to exchange a portion of the cationsrepresented by M or indeed substantially all of the cations representedby M in the second bracket for some other preselected cation or mixtureof cations. The partial hydroxides of aluminum are exchangeable withdifficulty, if at all. Thus, for example, referring to the first generalformulation given hereinabove, the charge-balancing cation C can at willbe selected from such diverse species as palladium, hydroxyaluminum,hydroxynickel, trimethylammonium, alkyl phosphonium, and the likecations and indeed mixtures thereof. Thus, C may be selected from thegroup consisting of alkaline earth metal, heavy metal, heavy metalpartial hydroxides, ammonium, substituted ammonium, substitutedphosphonium, and the like cations and mixtures thereof. As noted above,alkali metals are preferably excluded but may be present in minoramounts.

In the case of the use of substituted ammonium and substitutedphosphonium ions and the like, the substituents should be such that theycan be driven off during calcination of the mineral.

Those skilled in the art will recognize, accordingly, that the firstbracket of the above formula relates to a fixed array of ions in atripartite lamina which for convenience may be described asmuscovite-like, and in which the positive ions shown in the firstparentheses are octahedral coordination with sheets comprising oxygen,hydroxyl, and fluoride ions; whereas the positive ions shown in thesecond parentheses in the first bracket are in tetrahedral coordinationjointly with the aforesaid sheets of oxygen, hydroxyl, and fluorideions, and also with sheets of oxygen ions in essentially a hexagonalring array constituting the external faces of the tripartite lamina. Thepositive ions shown in the second bracket have no essentially fixedposition, but are in effect external to the lattice of the tripartitelamina.

Those skilled in the art will also recognize that when some of theparameters in the above formulations have values outside of thestipulated ranges, the formulations reduce to representations of variousend members of a broad group of laminar aluminosilicates, which ofcourse are outside of the scope of the present invention. Thus, forexample, when w and x both equal zero, and no fluoride ion is present,the first bracket describes the mineral pyrophyllite. It will also beseen that the factor d is equal to zero, when w and x equal zero, sothat the ionic species set forth in the second bracket are not present,which of course results from the fact that the lattice of pyrophylliteis charge-balanced. Again, for the case in which x equals zero, w equals2, e equals 2, and no fluoride is present, a mineral results in whichthe lattice is likewise charge-balanced, and the ionic species set forthin the second bracket are not present. Such a mineral is described inU.S. Pat. No. 2,658,875 to Cornelis et al.

In general, 2:1 layer-lattice aluminosilicate minerals, or inalternative nomenclature, tripartite aluminosilicate minerals of thetype concerned in the present invention, may be classified as eitherdioctahedral or trioctahedral, depending upon whether the number ofcations per unit cell in the octahedral (or inner) layer isapproximately 4 or 6, respectively. The foregoing structural formula is,as stated, an overall formula for a given preparation, and the fact thatthe number of such octahedral cations may vary from 4 to 6 in acontinuous manner in the formulation given does not mean that a singlelamina is present having such an intermediate number of cations. Inpoint of fact, the individual laminae are believed to be eitherdioctahedral or trioctahedral, and in a given preparation the relativeproportions of the dioctahedral and trioctahedral species will give riseto the numerical values obtained in quantitatively characterizing thepreparation in accordance with the foregoing formula. Where e in theformulation is intermediate between 2 and 3, accordingly, both 1:1 and3:2 substitutions are present. Because of the extremely small particlesize of the minerals, the exact physical nature of these mixed phasesystems is uncertain. In any case, in this specification, the term "amineral" shall mean the 2:1 layer lattice products which are produced bysimultaneously synthesizing both the dioctahedral and trioctahedralphases in place in a single reaction mixture. It may be emphasized thatsuch mineral made for use in this invention is a single mineral species,even though it may contain two phases. The minerals of this invention,therefore, differ significantly from compositionally similar mixturesobtained by simply mixing together the separately synthesizeddioctahedral and trioctahedral members.

The minerals in accordance with the invention are synthesized by ahydrothermal route, detailed examples of which will be given later. Theprocedure follows in a general way that set forth in U.S. Pat. No.3,252,757 to W. T. Granquist, except that the cited patent does notrelate to the inventive aluminosilicates, which contain additionalelements, so that the reaction mixtures required in the presentinvention are substantially different. As will be evident from thestructural formula already given, the reaction mixture for thehydrothermal synthesis includes a source of one or more multivalentcations other than aluminum and silicon. For example, for the case ofnickel, this may be relatively soluble compound, such as, for example,nickel acetate, nickel fluoride, nickel nitrate, and the like; or it maybe a relatively insoluble nickel compound such as a nickel hydroxide. Itis of interest that in general the inclusion of soluble nickel salts inthe reaction mixture tends to cause the nickel to occur predominantly inthe trioctahedral phase, while relatively insoluble nickel compoundspromote its occurrence in the dioctahedral phase. The terms are wellunderstood in the art, and a brief explanation in addition to thatalready given may be found on page 156 of the book by George Brown, "TheX-Ray Identification and Crystal Structures of Clay Minerals", London1961. The classical paper by Ross and Hendricks, "Minerals of theMontmorillonite Group", U.S. Geological Survey Professional Paper 205-B(1945) is helpful, particularly for its treatment of variation of themembers of a given series of laminar aluminosilicate minerals.

For the other elements useful in practicing the invention, such ascobalt, the most commonly available simple inorganic and organiccompounds thereof may in general be used, as will be evident to thoseskilled in the art.

The minerals after their preparation are activated for use as catalystsby drying and calcining. By drying is meant the removal of the externalwater of absorption by heating. Usually the drying temperatures are from250° to 350°F. at atmospheric pressure, albeit higher and lowerpressures can, of course, be employed. By calcining is meant theaddition of heat to effect some chemical change in the catalyst such asthe removal of chemically bound water or ammonia if the charge-balancingcation is NH₄ ⁺. The calcining temperatures are normally from about800°F. to about 1300°F. Atmospheric pressure is usually employed buthigher or lower pressures can, of course, be used. The maximumcalcination temperature should be below that temperature wherein a phaseinversion may occur. Thus, dehydration of the dioctahedral phase maypreferably occur at normal calcination temperatures but increasedtemperatures tend to result in dehydration of the trioctahedral phasewhich may then recrystallize to form a new undesired mineral species.Minor amounts of ammonium, substituted ammonium, etc. type ions whichcan be changed during the drying and calcining cycle may remain. UsuallyC in the above formula after drying and calcining is selected from thegroup consisting of H⁺, a multivalent metal cation or the partialhydroxide of a multivalent metal cation.

The heat activated minerals are suitable in accordance with theinvention as catalysts for the conversion of hydrocarbon charge stocksin the presence of hydrogen but these materials tend to age more quicklythan desired. In accordance with another aspect of this invention, animproved catalyst comprises the minerals described above containing, inaddition, a hydrogenation component deposited thereon. Any suitablehydrogenation component can be employed. For example, a suitablehydrogenation component would be one or more metals from Groups VIand/or VIII of the Periodic Table. These metals or combinations ofmetals are deposited on the heat activated minerals described above anddo not form a part of the mineral structure as do the Y and Q definedmetals. The deposited metals can be in the form of metals, metalsulfides or metal oxides or mixtures thereof.

The method of deposition of the hydrogenation component is not criticaland any method well known in the art can be employed, such as, forexample, the deposition of the hydrogenation component onto a dried orheat activated mineral from a solution of the aqueous salts of themetals. The technique of minimum excess solution can suitably beemployed, or an aqueous solution of the desired metal, such as palladiumnitrate, can be added to an aqueous slurry of the formed mineral withoutintermediate drying or calcining. The hydrogenation component can alsobe added using techniques known in the art for exchanging metal ionswith solid inorganic exchanges, such as zeolites. Also, thehydrogenation component can be added as a result of the reaction of ametal salt with the base material especially when [dC^(Y) ] is H⁺ or NH₄⁺. For example, if NiCl₂ is intimately mixed in the dry state with thehydrogen form of the structure on page 2, and then heated, HCl can beevolved with the result that Ni is dispersed uniformly throughout thestructure.

After the deposition of the hydrogenation component, the composition issuitably activated by drying under the usual conditions following bycalcining, again under the usual conditions.

The preferred hydrogenating components are nickel, cobalt and theplatinum group metals, and in particular palladium.

The amount of the hydrogenation component will depend somewhat on themetal or combination of metals chosen. The platinum group metals areusually used in concentration of 0.01 to 5 weight percent of the finalcatalyst, usually from 0.10 to 1.0 weight percent. The other metals fromGroups VI and VIII are normally used in higher concentrations on theorder of 0.2 to 20 weight percent.

For ease of discussion, the following description will refer to nickel,but it is to be understood that any metal or mixture of metals includedwithin the definition of Y is meant.

Some specific examples of the synthesis of minerals will now be given.From these examples, the general procedure will be clear, and it may benoted that if one desires a higher or lower ratio of nickel to silicon,or a higher or lower ratio of aluminum to silicon in the final product,the relative proportions of these components in the reaction mixtureshould be adjusted accordingly.

EXAMPLE 1

346 g. of hydrated alumina, Al₂ O₃.3H₂ O (Alcoa C 31, 64.9% Al₂ O₃) wereadded with stirring to a polysilicic acid sol which was prepared bypassing sodium silicate solution over a hydrogen-resin. The volume ofsol was chosen so as to contain 317 g. SiO₂. 8.95 g. of NH₄ F.HF werethen dissolved in this silica-alumina slurry. In a separate vessel, 19.1g. of NiF₂. 4H₂ O were dispersed in 63.0 g. of an ammonium hydroxidesolution assaying 58.8% NH₄ OH. This ammoniacal slurry was then added tothe silica-alumina dispersion, with stirring. If gel formation occurred,sufficient water was added to break the gel so that efficient stirringcould continue. The final feed slurry, with a pH 8.5, was charged to a1-gallon stirred autoclave, heated quickly (1 to 11/2 hr.) untilpressure line-out at 1240 psig (300°C.) and maintained at thistemperature and pressure for three hours. The product was cooled in thepressure vessel, removed, sheared in a blender to insure homogeneity,and a small quantity dried for analysis. The product slurry had a pH =7.4. The dried sample had a total nickel content of 1.30% (as Ni); thenon-exchangeable Ni content was 1.2%. The sample gave an X-raydiffraction pattern typical of 2:1 layer-lattice silicates.

Pd was placed on the clay by adding to 1535 g. of product slurry asolution which contained 4.185 g. of (NH₄)₂ PdCl₄ dissolved in 125 ml ofdeionized water. The slurry was stirred (with mild agitation) overnightat room temperature, and then filtered. The filter cake was washed twiceby redispersion in deionized water and refiltrated. The final filtercake was air-dried at 110°C., cooled, and crushed to 10/20 meshparticles. The final catalyst contained 1.4% Ni and 0.8% Pd.

EXAMPLE 2

This synthesis was similar to Example 1, described above, except thatthe proportions of the starting materials were altered to yield a clayof approximately 10% Ni content. The feed slurry was composed of 2890 g.of polysilicic acid sol (which contained 5.2% SiO₂), 164 g. Al₂ O₃.3H₂O, 95.5 g. NiF₂.4H₂ O and 42.7 g. of NH₄ OH solution (which contained47% NH₄ OH). The feed and product pH were 8.4 and 8.5, respectively. Thetotal nickel content of the product was 11.1% (as Ni); thenon-exchangeable nickel content was 9.9%. Pd was added as previouslydescribed; the finished catalyst contained 10.1% Ni and 0.8% Pd.

EXAMPLE 3

25 pounds of SiO₂ (as polysilicic acid sol assaying 5.2% SiO₂) werepumped into a feed mix tank equipped with an efficient high-torquestirring system. To this silica sol were added with stirring 27.3 poundscommercial trihydrate of alumina (which assayed 64.9% Al₂ O₃), 23.5pounds of nickel acetate.4-hydrate (which contained 23.7% Ni) previouslydissolved in 10 gal H₂ O and 1.24 pounds of NH₄ F.HF (purity of 96%)already in solution in 1 gal H₂ O. With continued stirring, sufficientaqua ammonia was added to bring the slurry pH to 8. This pH adjustmentwas accomplished with 13 pounds of aqua ammonia, which contained 48% NH₄OH. The final volume of slurry was about 75 gal.

After approximately 10 hr. of agitation, the feed slurry was pumped intoa 100 gal jacketed autoclave, heated by electric heaters immersed inDowtherm. The autoclave was sealed and heating started. After 12 hr. 45min., temperature lined out at 300°C. and a pressure of 1240 psig. Thecontents were maintained at these conditions for 4 hours at which timedrawdown through a quench condenser and expansion valve was started.Total time for discharge was 1 hour. A small sample was dried, examinedand found to be a 2:1 layer-lattice aluminosilicate which contained 9.6%Ni. A portion of the product was retained as slurry for after-treatmentby Pd impregnation as previously described.

EXAMPLE 4

143.5 g. of hydrated alumina, Al₂ O₃.3H₂ O (Alcoa C 31, 64.9% Al₂ O₃)were added with stirring to a polysilicic acid sol which was prepared bypassing sodium silicate solution over a hydrogen-resin. The volume ofsol was chosen so as to contain 150 g. of SiO₂. 7.43 g. of NH₄ F.HF werethen dissolved in this silica-alumina slurry. 94.5 g. of Ni(Ac)₂.4H₂ Owere dissolved in a minimum amount of water, added to the above slurry,and 29.8 g. of aqua ammonia (assaying 58.8% NH₄ OH) were added withstirring. If gel formation occurred, sufficient water was added to breakthe gel so that efficient stirring could continue. The proper volume ofthe final feed slurry was charged to a one-gallon stirred autoclave,heated quickly (1 to 11/2 hrs.) until the pressure lined out at 1250psig (300°C.) and was maintained at this temperature and pressure for 3hours. The product was cooled in a pressure vessel, removed, sheared ina blender to insure homogeneity and dried at about 250°F. Palladium wasadded to the dried product by impregnation in the same manner asdescribed in Example 1, and the final catalyst contained 6.75% Ni and0.56% Pd.

EXAMPLE 5

Example 4 was repeated except using 131 g. of hydrated alumina, 120 g.of SiO₂, 5.68 g. of NH₄ F.HF, 130 g. of aqua ammonia and 113 g. ofcobalt acetate (Co(Ac)₂.4H₂ O) in lieu of nickel acetate. The finalcatalyst contained 7.36% cobalt and 0.64% palladium.

While the products are somewhat well crystallized, the actual size ofthe crystal does not lend itself readily to characterization by theolder methods of optical crystallographic methods. Much more precise arethe results obtained by X-ray diffraction, and by way of furthercharacterization of the products in accordance with the invention, therefollow tabulations of spacings and intensities obtained on a number ofmineral products having chemical compositions embraced by the earlierformula. Tables I-IV inclusive show such X-ray diffraction data for twoseries of products made along the lines indicated in Examples 1-4inclusive.

The products tabulated in Table I consist, except at the end members, ofmixed di- and trioctahedral phases. The Ni-free end member is "pure"dioctahedral; the Ni₆ sample is pure trioctahedral. In the intermediaterange, the amount of trioctahedral phase increases with the Ni/unitcell. The products summarized in Table III are pure trioctahedral.

In the series shown in Tables I and II, the aluminum (IV) content washeld constant at one and one-half atoms per unit cell while the nickelcontent was varied from zero to six atoms per unit cell. A summary ofthe results obtained is given in Table I with a more detailed tabulationfollowing in Table II. It will be understood that the first number ofthis series, in which no nickel is present at all, is outside of thescope of the invention; the results are shown merely for comparativepurposes.

In the series for which results are given in Tables III and IV, thenickel content was held constant at six atoms per unit cell, while thetetrahedral aluminum was varied from zero to two atoms per unit cell.Here again, the first number of the series, containing no aluminum, isoutside of the scope of this invention and the results are included inthe tabulation for comparative purposes. Table III is a summary, andTable IV shows the results in detail for each member of the series.

                                      TABLE I                                     __________________________________________________________________________    SUMMARY                                                                       Ni VARIABLE, x = 1.5                                                          d, A (d spacings in A)                                                        Ni/u.c.                                                                              0     1/8  1      2      3      4    5    6                            __________________________________________________________________________    Index*                                                                        OOl                                                                           001    10.6  11.8 11.3   11.3   13.0.sup.b                                                                           13.4.sup.b                                                                         13.4.sup.b                                                                         13.6.sup.b                   002    5.18  5.68 5.34   5.24   --     --   --   --                           003    3.41  3.26 3.37   3.34   --     --   --   --                           004    --    --   --     --     3.30   3.26 3.24 3.29                         005    2.061  2.065                                                                             --     --     --     --   --   --                           hk                                                                            11;02  4.46  4.46 4.50   4.48   4.48   4.50 4.55 4.54                         13;20  2.57  2.56 2.58   2.57   2.58   2.58 2.61 2.58                         31;15;24                                                                             1.691  1.687                                                                              1.699 1.67    1.691 --   --   --                            06    1.499  1.492                                                                               1.517).sup.a                                                                         1.522).sup.a                                                                         1.522).sup.a                                                                        1.522                                                                              1.524                                                                              1.522                                          1.502)                                                                               1.502)                                                                               1.500)                                       hkl                                                                           131 (Prob.)                                                                          2.453 2.45  2.453 2.42    2.466 2.47 --   2.51                         __________________________________________________________________________     *Significant peaks only. See detailed tables for intensity data. Basal        sequence may involve mixed layering. If so, indices would be mixed; e.g.      003/004.                                                                      .sup.a Doublet consisting of di- and trioctahedral components.                .sup.b Probably intercalated acetate.                                    

                  TABLE II(a)                                                     ______________________________________                                        Ni VARIABLE, x = 1.5 (EXPECTATION VALUE).sup.a                                Ni = 1/8 u.c.                                                                        Probable                                                               d,A    Index     Height, mm   Comment                                         ______________________________________                                        11.8   001/001   172            Strong,Symmetrical                            5.68   002/002.sup.c                                                                           18             Weak, Symmetrical                             4.46   11;02     148    5.5 mm, Strong,Asymmetrical                                                   w/2.sup.b                                             3.26   003/004   48             Symmetrical                                   2.56   13;20     65             Asymmetrical                                                                  (band, 2.31-2.62)                             2.45   hk        36             Shoulder                                      2.065  00l.sup.c 18             Symmetrical                                   1.687  31;15;24  20             Asymmetrical                                  1.492  06        42     12 mm,                                                              w at h/2.sup.d                                                                         Slightly                                                                     Asymmetrical                                            ______________________________________                                         .sup.a Expectation Value in this and other Tables means the value of x        based on the starting compositions.                                           .sup.b w/2 in this and other Tables means half-width at baseline. For         asymmetrical peak, smaller distance.                                          .sup.c Uncertain due to complications due to mixed layering.                  .sup.d w at h/2 in this and other Tables means half-height.              

                  TABLE II(b)                                                     ______________________________________                                        Ni = 1/u.c.                                                                           Probable                                                              d,A     Index    Height, mm  Comment                                          ______________________________________                                        11.32   001/001  140           Strong,well defined                            5.34    002/002  11            Weak, Symmetrical                              4.50    11;02    147    7.5 mm,                                                                              Asymmetrical, Sharp                                                    w/2                                                   3.37    003/004.sup.a                                                                          47            Symmetrical, Broad                             2.583   13;20    102           Asymmetrical,                                                                 Mod. sharp                                     2.453   hk       56            Symmetrical                                    1.699   31;15;24 17            Asymmetrical, Broad                             1.517) 06       22            (Doublet -- 1.517 is                            1.502)          48            a shoulder on low-                                                            angle side of 1.502                            ______________________________________                                         .sup.a Uncertain due to complications due to mixed layering.             

                  TABLE II(c)                                                     ______________________________________                                        Ni = 2/u.c.                                                                           Probable                                                              d, A    Index     Height, mm  Comment                                         ______________________________________                                        11.32   001/001   135           Not well defined                              5.24    002/002   6             Symmetrical                                   4.48    11;02     122    6 mm,  Strong, sharp,                                                         w/2    asymmetrical                                  3.34    003/004   40            Symmetrical, broad                            2.57    13;20     93            Asymmetrical, Mod.                                                            sharp                                         2.42    hk        55            Asymmetrical                                  1.67    31;15;24  13                                                           1.522) 06        35            (Doublet -- about                              1.502)           35            (equal height;                                                                (trioct. dioct.                               ______________________________________                                    

                  TABLE II(d)                                                     ______________________________________                                        Ni = 3/u.c.                                                                           Probable                                                              d, A    Index     Height, mm  Comment                                         ______________________________________                                        13.0    001/001.sup.a                                                                           190           May have inter-                                                               calated acetate                               4.48    11;02     90     11 mm, Asymmetrical                                                           w/2                                                  3.30    003/004.sup.a                                                                           40            Broad, symmetrical                            2.576   13;20     96            Mod. sharp,                                                                   asymmetrical                                  2.466   hk        61            Ill-defined                                   1.691   31;15;24  15            Broad                                          1.520) 06        53            (Doublet -- 1.500 A                            1.500)                         (a shoulder on                                                                (high angle side                                                              (of 1.520 trioct.                             ______________________________________                                         .sup.a Uncertain due to complications due to mixed layering.             

                  TABLE II(e)                                                     ______________________________________                                        Ni = 4/u.c.                                                                          Probable                                                               d, A   Index     Height, mm  Comment                                          ______________________________________                                        13.4   001/001.sup.a                                                                           201           Ill-defined -- may                                                            have intercalated                                                             acetate                                        4.50   11;02     56     14 mm, Asymmetrical                                                           w/2                                                   3.26   00        38            Broad,symmetrical                              2.58   13;20     86            Asymmetrical                                   2.47   hk        58            Broad shoulder on                                                             2.58                                            1.522 06        67            Asymmetrical -- tail-                                                         ing toward high                                                               angle side                                     ______________________________________                                         .sup.a Uncertain due to complications due to mixed layering.             

                  TABLE II(f)                                                     ______________________________________                                        Ni = 5/u.c.                                                                           Probable                                                              d, A    Index     Height, mm  Comment                                         ______________________________________                                        13.4    001       200          Uncertain height --                                                           not well defined                               4.55    11;02     58    9 mm,  Asymmetrical                                                           w/2                                                   3.24    00        45           Symmetrical                                    2.61    13;20     90           Asymmetrical -- band                                                          head band extends                                                             2.64 1.97 A                                    1.524   06        87           Asymmetrical --                                                               tails toward high                                                             angle side                                     ______________________________________                                    

                  TABLE II(g)                                                     ______________________________________                                        Ni = 6/u.c.                                                                           Probable                                                              d, A    Index     Height, mm   Comment                                        ______________________________________                                        13.6    001.sup.a 192            Poorly defined -- may                                                         be intercalated                                                               acetate                                      4.54    11;02     59     9 mm w/2                                                                              Asymmetrical                                 3.29    004.sup.a 40             Very broad,                                                                   symmetrical                                  2.58    13;20     83             Broad, band-head of                                                           band extending                                                                from 2.64  1.97 A                            2.51    hk        84             Part of above band                           1.522   06        98     14 mm,  Mod. sharp asymm.                                                     width   tailing to high                                             at h/2  angle side                                             ______________________________________                                         .sup.a Uncertain                                                         

                  TABLE III                                                       ______________________________________                                        SUMMARY                                                                       Ni = 6, x = VARIABLE                                                          Al.sup.IV /u.c.                                                                        0        1/2      1      1.5    2                                    ______________________________________                                        Index*                                                                        00l                                                                           001      9.6      11.6     13.4.sup.a                                                                           13.6   --                                   002      --       --       --     --     --                                   003       3.145   --       --     --     --                                   004      --       3.25     3.32   3.29   3.42                                 005      --       --       --     --     --                                   hk                                                                            11;02    4.55     4.55     4.56   4.54   4.53                                 13;20    --       2.62     2.59   2.58   2.62                                 22;04    2.27     --       --     --     --                                   31;15;24 --       --       --     --     --                                   06        1.522    1.522    1.524  1.522                                      hkl                                                                           131      2.51     --       --     2.51   2.51                                 (Prob)                                                                        ______________________________________                                         *Significant peaks only. See detailed tables for intensity data.               Basal sequence may involve mixed-layering. If so, indices would be mixed     e.g., 003/004. Also, possible intercalation of acetate may affect 00l.        .sup.2 This particular sample, when oriented and glycol treated, gave an      ool of 17.7 A.                                                           

                  TABLE IV(a)                                                     ______________________________________                                        Ni = 6, x = 2.0 (Expectation Value)                                                  Probable                                                               d, A   Index     Height, mm    Comment                                        ______________________________________                                        4.53    11;02    48.5            Asymmetrical                                 3.42   004.sup.a 46              Broad, symmetrical                           2.62    13;20    83      14 mm,  Very broad, part                                                      w/2     of band extending                                                             from 2.64 A 1.97                             2.51   hk        85              Very broad; part                                                              of same band                                  1.526 06        78      16 mm   Moderately sharp;                                           at h/2  slightly asym-                                                                metric                                                 ______________________________________                                         NOTE: 00l is not defined; slight trade of kaolinite-like phase at 7.08 A.     .sup.a Uncertain.                                                        

                  TABLE IV(b)                                                     ______________________________________                                        x = 1.5 (Expectation Value)                                                          Probable                                                               d, A   Index    Height, mm    Comment                                         ______________________________________                                        13.6    001     192             Poorly defined                                4.54    11;02   59      9 mm,   Asymmetrical                                                          w/2                                                   3.29   004.sup.a                                                                              40              Very broad,                                                                   symmetrical                                   2.58    13;20   83              Broad, part of band                                                           extending from                                                                2.64   1.97 A                                 2.51   hk       84                                                             1.522 06       98.5    14 mm   Moderately sharp;                                                     w at h/2                                                                              slightly asym-                                                                metric                                        ______________________________________                                         .sup.a Uncertain.                                                        

                  TABLE IV(c)                                                     ______________________________________                                        x = 1.0 (Expectation Value)                                                           Probable                                                              d, A    Index    Height, mm    Comments                                       ______________________________________                                        13.4.sup.a                                                                            001      191             Well defined on                                                               oriented slide;                                                               poorly defined on                                                             random slide                                 4.56     11;02   61     11 mm,   Asymmetrical                                                         w/2                                                   3.32    004.sup.b                                                                              41              Very broad,                                                                   symmetrical                                  2.59    13;20;   83              Asymmetrical band                                                             extending from                                                                2.661   1.97 A                               1.524   06       90     14 mm,   Moderately sharp;                                                    w at h/2 slightly                                                                      asymmetric                                   ______________________________________                                         .sup.a Expanded to 17.7 A with glycol treatment                               .sup.b Uncertain                                                         

                  TABLE IV(d)                                                     ______________________________________                                        x = 0.5 (Expectation Value)                                                          Probable                                                               d, A   Index     Height, mm   Comments                                        ______________________________________                                        11.6   001/001   224            Strong, well defined                          4.55   11;02     81     7 mm,   Asymmetrical                                                          w/2                                                   3.25   003/004   57             Broad, symmetrical                            2.62    13;20 hk 84             Band-head listed.                                                             Band extends 2.64                                                             1.97 A, asymmetri-                                                            cal                                            1.522  06       114    9 mm,   Sharp; slightly                                                       w at h/2                                                                              asymmetric                                    ______________________________________                                    

                  TABLE IV(e)                                                     ______________________________________                                        x = 0                                                                                Probable                                                               d, A   Index     Height, mm                                                                              Comments                                           ______________________________________                                        9.6    001       227       Very strong, well                                                              defined, symmetrical                              4.55   11;02      97 8 mm, Asymmetrical                                                          w/2                                                        3.145  003        93       Moderately sharp,                                                              symmetrical                                       2.51   13;20     106)      Band (strongly                                     2.27   22;04      47)       asymmetrical                                                                  2.64   1.97 A                                     1.522   06       120 8 mm, Sharp, slightly                                                     w at h/2   asymmetric                                        ______________________________________                                    

From size considerations alone, Ni² ⁺ is expected to occupy octahedralsites and to be excluded from tetrahedral sites in the layer structure,or to occupy charge-balancing sites either as Ni² ⁺ or as ahydroxy-nickel species. Al³ ⁺, however, can occupy octahedral,tetrahedral, or charge-balancing sites; in the latter case, ahydroxy-aluminum species is to be expected. The diffraction data in theprevious tables show 06 reflections typical of mixeddioctahedral/trioctahedral minerals. Furthermore, the trioctahedral 06(>1.505 A) peak height increases, and the dioctahedral 06 (<1.505 A)decreases, as the overall average Ni per unit cell varies over the range0 to 6. In addition, reference is made to the attached FIG. 1 whereinthe intensity of the trioctahedral 06, corrected for change in the massabsorption coefficient as Ni increases and Al decreases, is plotted as afunction of the expected overall average level of Ni, i.e. the expectedoverall average Ni per unit cell based on feed composition. In FIG. 1,h(06_(tri) ) is the 06 peak height in chart units; μ/ρ is the massabsorption coefficient in the "Ni per unit cell (average)" to 3w asdefined in the empirical formula. Note the intensity is a linearfunction of the amount of Ni per unit cell and that the lineextrapolates to zero intensity at zero nickel level. The equation forthe intensity of the 06 line of the trioctahedral phase (I₀₆(trioct)) isgiven on FIG. 1 as equal to k(3w) where k is a constant. The curve inFIG. 1 is the best fit for values of x from 0.5 to 1.45. For thisparticular system, any amount of nickel added (within the compositionallimits) crystallizes as a trioctahedral nickel silicate which may or maynot contain 4- coordinated Al. Thus, in this system, any mixture of NiOand Al₂ O₃ which contains less than the amount of Ni required for 6 Niper unit cell will form mixed dioctahedral-trioctahedral phases.

It will be helpful to outline a procedure by which it may be determinedif a given preparation falls within the scope of the claimed mineralsbefore drying and calcining.

First, x-ray diffraction must establish the material in question to be a2:1 layer silicate by procedures well known to those skilled in the art.Of particular help in this instance would be pertinent subject matter inthe text by G. Brown, cited hereinabove. The material being examinedshould be substantially free of accessory phases.

It is then necessary to obtain a total analysis of the sample, expressedas the oxides of the cations in their original oxidation states.Suitable analytical methods are discussed in Furman, N. H., Ed "Scott'sStandard Methods of Chemical Analysis", 6th Ed. Van Nostrand, New York(1962), Vol. I, Chapter 41. If fluoride is present, the percent oxidesplus percent fluoride is corrected by substracting the percentage offluoride ion multiplied by the quotient of the equivalent weight ofoxygen ion divided by the equivalent weight of fluoride ion. Adequacy ofthe analysis is indicated if this corrected total lies between 99.5% and100.5%. The analysis is recalculated as charge equivalents (i.e., cationequivalents x cation charge), normalized to charges per 44 charges (thenegative charge per unit cell of the oxygen-hydroxyl framework of the2:1 layer silicates) and finally expressed as cations per unit cell(e.g., the silicon charges per 44 charges divided by the charge of thesilicon cation). These cations are then distributed over the tetrahedraland octahedral layers in accord with the tabulated lists of cationsfalling into the categories Y and Q. In this way the values of thevarious subscripts in the general formula can be obtained. Examples ofthis technique, a statement of the rules for cation distribution, and adiscussion of the uncertainties involved and the meaning of the resultscan be found in Kelly, W. P., "Interpretation of Chemical Analyses ofClays", Clays and Clay Technology, Bulletin 169 of the CaliforniaDivision of Mines (1955), pp. 92-94; and Osthaus, B.B., "Interpretationof Chemical Analyses of Montmorillonite", same reference, pp. 95-100.

An illustrative example follows. This particular example has beenselected to include the complexities arising from mixed di- andtrioctahedral phases, mixed 1:1 and 3:2 substitution octahedrally, andmixed 4- and 6-fold coordinated aluminum ion.

Chemical analysis and charge data for a chosen mineral are summarized inTable C below:

                  TABLE C                                                         ______________________________________                                                                         Charges                                                       Cation   Charge per 44 Cations/                              Component                                                                             Analysis Equiv.   Equiv. Charges                                                                              u.c.                                  ______________________________________                                        SiO.sub.2                                                                             50.59    0.842    3.37   27.59  6.90                                  Al.sub.2 O.sub.3                                                                      23.33    0.458    1.37   11.25  3.75                                  NiO     16.86    0.226    0.451  3.70   1.85                                  (NH.sub.4).sub.2 O                                                                    4.61     0.177    0.177  1.45   1.45                                  F       2.09     0.110    --     --     --                                    H.sub.2 O                                                                             3.41                                                                          100.89            5.369  43.99                                        F .tbd. O.sup.1                                                                       - 0.88                                                                Corr.                                                                         Total   100.01                                                                ______________________________________                                         .sup.1 Fluoride equivalent to oxygen                                     

Referring to the information in Table C, calculations can be made toshow the distribution of cations in the tetrahedral and octahedrallayers. All of the silicon is assumed to be in the tetrahedral layer andis equal to 6.90 cations per unit cell. Since there are 8 cations perunit cell in the tetrahedral layer, the number of aluminum cations perunit cell must be 1.10. It is also known that there are 32 charges inthe tetrahedral layer. Because there is some Al⁺ ³ in the tetrahedrallayer rather than Si⁺ ⁴, there is a negative charge in the tetrahedrallayer of 1.10. The aluminum distributed in the octahedral layer iscalculated by difference to be 2.65 cations per unit cell, and thenickel by analysis is shown to be 1.85 cations per unit cell. Since itis known that the octahedral layer has 12 charges per unit cell,calculations show that the octahedral layer has a net negative charge of0.35. The total net negative charge is 1.45, which is balanced by theinterlayer NH₄ ⁺ charge of 1.45 cations per unit cell to give anelectrostatically neutral product.

From the tabulated calculation, x in the general formula is 1.10, 3w is1.85, and ew = 4-2.65 = 1.35, so that e = 2.19. The value of f can beobtained by noting F/Si = f/(8-x) = 0.131. Since x equals 1.10, then f =0.90. The coefficient, d, of the amount of exchange ion (NH₄) is 1.45.Therefore, the average formula for this example is

    [(Al.sub.2.65 Ni.sub.1.85).sup.VI (Si.sub.6.90 Al.sub.1.10).sup.IV O.sub.20 (OH).sub.3.1 F.sub.0.9 ] 1.45NH.sub.4

comparison of the defined ranges of x, e, w, f, and d and the ions whichcan fill the roles of Y, Q and C with the results shown abovedemonstrates that the example falls within the scope of the definedformula.

An alternate method of calculation is based on the use of ionic ratios.However, the method is still dependent on the aluminum distributionbetween 4- and 6-fold states.

Let:

R₁ = si/Al = (8-x)/(4-ew) + x

R₂ = si/Ni = (8-x)/ 3w

R₃ = al^(IV) /Al^(VI)

and

R₄ = f/si = f/(8-x).

Then it can be shown that:

    x = 8R.sub.3 /R.sub.1 R.sub.3 + R.sub.1 + R.sub.3          (1)

    w = (8-x)/3R.sub.2                                         (2)

    e = (4R.sub.3 -  x)/ w R.sub.3                             (3)

and

    d (if exchange cation is monovalent) = x + (e-2)3w         (4)

Once x is obtained from the ratios and equation (1), w can be calculatedaccording to equation (2); e from equation (3) with x and w; and finallyd from equation (4). From the analysis given, R₁ = 1.84; R₂ = 3.73; andR₄ = 0.131. From the distribution given, R₃ = 0.416. Thus, x = 1.10; w=0.617; e = 2.19; and d = 1.45 from equations (1) through (4), in goodagreement with the values obtained by the distribution procedure. Thevalue of f can be recovered from R₄ as shown above. This calculation ispresented simply to show the validity of equations (1) through (4).Given such validity, any analytical method or combination of methodsthat provides accurate values of the required ratios will give thecorrect values of x, w, e, and d.

As noted above, the heat activated minerals are suitable as catalystsfor the conversion of hydrocarbon charge stocks in the presence ofhydrogen. By a "hydrocarbon conversion process" is meant a conversion ofhydrocarbons in the presence of hydrogen to some configuration differentfrom the configuration of the starting hydrocarbons. Such change ofconfiguration may be the result of isomerization (e.g., straight-chainparaffins to branch chain paraffins); dehydrogenation (e.g., naphthenesto aromatics); saturation (olefins to paraffins); hydrocracking (higherboiling hydrocarbons to lower boiling hydrocarbons); desulfurization;dehydrocyclization; and reforming. A hydrocarbon conversion process maybe either hydrogen consuming or hydrogen producing. The addition and useof hydrogenating components to the heat activated minerals is alsocontemplated, and it will be obvious to those having ordinary skill inthe art which hydrogenation components to distend upon the heat treatedminerals in light of the particular reaction of interest. Similarly,those having ordinary skill in the art will understand the range ofoperating conditions at which the reaction of interest should beconducted since hydrocarbon conversion process, per se, as defined aboveare well known in the art.

The invention will be further described with reference to the followingexperimental work.

HYDROISOMERIZATION

The catalysts of this invention are particularly useful for thehydroisomerization of aliphatic hydrocarbons having from 4 to 10 carbonatoms per molecule under hydroisomerization conditions. The catalystsfor isomerization are preferably prereduced with hydrogen but reductionof the catalysts can, of course, occur in situ. The catalysts have alsobeen found to tolerate small concentrations of aromatics, olefins,sulfur and water normally present in feeds such as natural gasoline.

Suitable hydroisomerization conditions include a temperature from 300°F.to 750°F., preferably 425°F. to 600°F.; a pressure of 100 to 10,000psig, preferably 200 to 2000 psig; a liquid hourly space velocity (LHSV)based on the hydrocarbon charge of 0.10 to 10 volumes of hydrocarboncharge per volume of catalyst per hour, preferably from 0.5 to 4.0v/v/hour; and a hydrogen to hydrocarbon mole ratio of from 0.5:1 to20:1, preferably from 2:1 to 5:1.

The hydroisomerization aspect of this invention will be furtherdescribed with reference to the following experimental examples.

EXAMPLE 6

The catalyst as prepared in Example 1 (1.4 weight percent nickelsubstitution) was calcined in air at 1000°F. for 10 hours and thenreduced in hydrogen at 650°F. for 16 hours. This catalyst was then usedas the catalyst for the isomerization of normal hexane by passage of thenormal hexane downflow through a bed of the catalyst at 550°F.; 1.5LHSV; 2.5 H₂ :n-hexane; and a total pressure of 450 psig. The hexaneconversion was 15 percent, with a 100 percent selectivity to C₆ isomers.The results of this run are summarized in Table V below.

EXAMPLE 7

Example 6 was repeated except the catalyst employed was the same as thatprepared in Example 1 above except sufficient additional nickel salt wasemployed to result in 2.4 weight percent nickel substitution. Thepercent hexane conversion was 30, with a 99 percent selectivity to C₆isomers. This Example is also summarized in Table V below.

EXAMPLE 8

Example 6 was repeated except the catalyst was the same as that shown inExample 2 above (10.1% nickel substitution). The percent hexaneconversion was 78, with 97 percent selectivity to C₆ isomers. ThisExample is also summarized in Table V below.

EXAMPLE 9

Example 8 was repeated except the reaction temperature was reduced to500°F. and the liquid hourly space velocity was reduced to 0.5. Thepercent hexane conversion was 68, while the percent selectivity to C₆isomers was 98. The results of this Example are summarized in Table Vbelow.

EXAMPLE 10

Example 9 was repeated except the reaction temperature was 450°F. andthe percent hexane conversion was 27, while the percent selectivity toC₆ isomers was 100. The results of this Example are summarized in TableV below.

EXAMPLE 11

Example 6 was repeated except the catalyst contained no nickelsubstitution in the lattice and was prepared in accordance with theteachings of U. S. Pat. No. 3,252,757. The catalyst was calcined andreduced prior to use under the same conditions as the catalyst forExample 6 above. The percent hexane conversion was 12, with 100 percentselectivity to C₆ isomers.

This Example is also summarized in Table V below.

EXAMPLE 12

Example 6 was repeated except the catalyst consisted of 0.7% palladiumand 15% nickel deposited by conventional impregnation techniques ontothe catalyst of Example 11. The percent hexane conversion was only one,with 100 percent selectivity to C₆ isomers. This Example is alsosummarized in Table V below.

EXAMPLE 13

Example 10 was repeated except the catalyst consisted of 1 percentpalladium deposited on a mordenite base in the hydrogen form. Thecatalyst was prepared by impregnating a commercially obtained hydrogenmordenite (purchased from the Norton Company) with a solution ofPd(NH₃)₄ (NO₃)₂ containing enough palladium salt to give 1.0 percentpalladium on the finished catalyst. The percent hexane conversion was 7with a percent selectivity to C₆ isomers of 100. The results aresummarized in Table V below.

EXAMPLE 14

Example 13 was repeated except the reaction temperature was increased to500°F. The percent hexane conversion was 24, with a percent selectivityto C₆ isomers of 100. This Example is summarized in Table V below.

EXAMPLE 15

Example 13 was repeated except the reaction temperature was 550°F. andthe liquid hourly space velocity was 1.5. The percent hexane conversionwas 31, and the percent selectivity to C₆ isomers was 98. The results ofthis run are summarized in Table V below.

EXAMPLE 16

Example 6 was repeated except the catalyst employed was the same as thecatalyst prepared in Example 3 above (9.6% Ni from nickel acetate). Thepercent hexane conversion was 50, while the percent selectivity to C₆isomers was 98. The results of this run are summarized in Table V below.

EXAMPLE 17

Example 16 was repeated except the catalyst of Example 16 was treatedwith HF to deposit 2 percent fluorine on the catalyst. The percenthexane conversion was 16, and the percent selectivity to C₆ isomers was99. The results of this run are summarized in Table V below.

Referring to Table V below, a comparison of the Examples illustrates theadvantage of including nickel in the lattice of the catalyst inaccordance with the teachings of this invention.

                                      TABLE V                                     __________________________________________________________________________    Hydroisomerization of N-Hexane at 450 psig                                                              Weight % Hexane                                                                    Selec-                                                       Reaction Conditions                                                                            tivity.sup.b                                   Ex.           Temp.   H.sub.2 :                                                                         Conver-                                                                            to C.sub.6                                     No.                                                                              Catalyst   °F.                                                                        LHSV                                                                              Hexane                                                                            sion.sup.a                                                                         Isomers                                        __________________________________________________________________________     6 0.7% Pd-1.4% Ni.sup.c                                                                    550 1.5 2.5 15    100                                            7 0.7% Pd-2.4% Ni                                                                          550 1.5 2.5 30     99                                            8 0.7% Pd-10% Ni                                                                           550 1.5 2.5 78     97                                            9 0.7% Pd-10% Ni                                                                           500 0.5 2.5 68     98                                           10 0.7% Pd-10% Ni                                                                           450 0.5 2.5 27    100                                           11 0.7% Pd- 0% Ni.sup.d                                                                     550 1.5 2.5 12    100                                           12 0.7% Pd-15% Ni.sup.e                                                                     550 1.5 2.5  1    100                                           13 1% Pd-H-mordenite                                                                        450 0.5 2.5  7    100                                           14 1% Pd-H-mordenite                                                                        500 0.5 2.5 24    100                                           15 1% Pd-H-mordenite                                                                        550 1.5 2.5 31    100                                           16 0.5% Pd-10% Ni.sup.f                                                                     550 1.5 2.5 50     98                                           17 0.5% Pd-10% Ni                                                                           550 1.5 2.5 16     99                                           __________________________________________________________________________    .sup.a Conversion calculated by weight of hexane recovered                     divided by the weight of hexane charged.                                     .sup.b Selectivity calculated by weight of C.sub.6 isomers produced            divided by the weight of C.sub.6 isomers which theoretically                  could have been produced.                                                    .sup.c Catalysts for Examples 6 through 10 prepared using                      NiF.sub.2 .4H.sub.2 O.                                                       .sup.d Base synthetic mica montmorillonite (SMM) prepared in                   accordance with teachings of U.S. Patent 3,252,757.                          .sup.e Catalyst for Example 12 prepared by impregnating Pd and                 Ni onto the base SMM containing 0% Ni (catalyst for Ex.11).              

The use of minor amounts of nickel in the lattice, for example, lessthan one percent, apparently has little effect on the activity of thecatalyst for hexane hydroisomerization. This can only be seen bycomparison of Examples 6 and 11 where the use of 1.4 percent nickel inthe lattice (Ex. 6) resulted in only a three percent hexane conversionadvantage over the same catalyst without nickel substitution in thelattice (Ex. 11). The percent hexane conversion decreases withdecreasing reaction temperature as expected (Exs. 8-10). The catalystsof this invention have about a 50°F. temperature advantage overpalladium on H-mordenite catalysts which are known for hexanehydroisomerization.

Referring to Table V above, a comparison of the Examples shows that forhexane hydroisomerization, the use of NiF₂ in the preparation of thenickel-substituted catalyst results in a more active catalyst than thecatalyst prepared using nickel acetate as the salt. It should be noted,however, that the nickel-substituted catalysts of this invention, evenwhen made from the nickel acetate salts, are still more active than thepalladium-H-mordenite catalyst (Ex. 16 compared with Ex. 15). Theaddition of fluorine to the catalyst prepared using nickel acetateappears to decrease the activity of the catalyst for hexane conversionunder the conditions shown in Example 17.

A further series of runs was made to study n-hexane hydroisomerization.In this series, the catalysts were prepared in a manner similar to thecatalyst preparation in Example 4 above, i.e. using the nickel acetatesalt. Varying amounts of nickel were substituted in the latticestructure by varying the amount of nickel acetate employed. Thecatalysts were calcined at 1000°F. for 10 hours and then reduced inhydrogen at 650°F. for 16 hours. The n-hexane was passed downflowthrough a bed of the catalyst at 500°F., 450 psig, a 1.0 liquid hourlyspace velocity based on the n-hexane, and an H₂ /n-hexane mole ratio of2.5. The results are shown in Table VI below:

                                      TABLE VI                                    __________________________________________________________________________                            Selectivity Wt %                                               Substituted                                                                            Hexane                                                      Ex.                                                                              Catalyst.sup.a                                                                      Nickel Atoms                                                                           Conversion                                                                          Isomerization 2,2 DMB/C.sub.6                         No.                                                                              Wt % Ni                                                                             Per Unit Cell                                                                          Wt %  to C.sub.6 Isomers                                                                     Cracking                                                                           Wt %                                    __________________________________________________________________________    18 0     0        3.5   100      --   <0.1                                    19 6.8   1        45    99       --   0.8                                     20 14.3.sup.b                                                                          2        71    94       6    4.1                                     21 15    2        76    96       4    8.7                                     22 15    2        74    95       5    6.4                                     23 21.6  3        80    95       5    13.4                                    24 26.4  4        84    79       21   14.4                                    25 30.5  5        86    73       27   19.9                                    26 35.7  6        85    76       24   18.8                                    A' 15.sup.c                                                                            0        0.9   100      --   <0.1                                    B' 15.sup.d                                                                            2        26    74       26   0.4                                     C' O.sup.e                                                                             0        33    98       2    3.5                                     __________________________________________________________________________    .sup.a All catalysts except Example B' contain from 0.5% to 0.7% Pd.          .sup.b This catalyst contained 0.61% fluoride compared to 1.01% for the       catalyst                                                                       for Example 21.                                                              .sup.c Catalyst of Example 12.                                                .sup.d Catalyst 21 without palladium.                                         .sup.e Catalyst of Example 13.                                            

Referring to Table VI, it can be seen that the hexane conversiongenerally increases with increased nickel in the lattice up to about 30%nickel. Similarly, the weight percent 2,2-dimethylbutane ("2,2-DMB") inthe product having six carbon atoms increased with increasing nickel inthe lattice to about 30% nickel. The weight percent 2,2-DMB wascalculated by dividing the weight of 2,2-DMB in the product by the totalweight of hydrocarbons in the product having six carbon atoms. Theconversion of hexane to one-branched isomers occurs readily compared tothe difficulty in the production of the double branched 2,2-DMB. Thus,as the percent nickel increases to about 30%, the catalysts are showingmuch more acidity, for the production of 2,2-DMB is really a measure ofthe surface acidity. The nickel is thus not functioning as surfacedeposited nickel but is part of the structure and lends itself toincreasing the surface acidity and thus to increasing the isomerizationactivity of the catalyst. In Example A' on Table VI above, the catalystof Example 12 was used (base synthetic mica montmorillonite having 0.7%Pd and 15% nickel deposited thereon by conventional impregnationtechniques) and the conversion was less than one percent. This resultshould be contrasted with the results in Examples 20 and 21 where about15% nickel was substituted in the lattice and conversions of about 75%were achieved with as much as 8.7 percent 2,2-DMB in the product.

Example B' in Table VI illustrates the importance of a hydrogenationcomponent on the base catalysts of this invention. Example B' uses thesame catalyst as in Example 21 except Pd is not deposited on thecatalyst, and the conversion of hexane drops as well as the efficiencyto the production of isomers. The selectivity to cracked productsincreased from 4 to 26 percent. Example B' shows the importance of usingpalladium along with lattice substituted nickel for excellentisomerization activity. To get good isomerization, both adehydrogenation function and an acid function are required. Thenickel-clay provides the acid function, and the impregnated Pd thedehydrogenation function.

Example C' in Table VI used a catalyst consisting of 1% palladiumdeposited on a commercially available H-mordenite zeolite. This is oneof the better catalysts available today for isomerization as noted bythe 98% selectivity to C₆ isomers. The conversion, however, isrelatively low as is the weight percent 2,2-DMB in the product.

A further run was made to study the hydroisomerization of a C₅ -C₆fraction of natural gasoline.

EXAMPLE 27

In the run for this Example, a C₅ -C₆ fraction of natural gasoline,whose properties are shown in Table VII below, was passed downflowthrough a bed of a catalyst the same as that employed in Example 25above. The reaction conditions included a temperature of 450°F., 450psig, a 0.5 liquid hourly space velocity, and a hydrogen to hydrocarbonratio of 2.5. The properties of the product are also shown on Table VIIbelow.

                  TABLE VII                                                       ______________________________________                                        Hydroisomerization of C.sub.5 /C.sub.6 Fraction of                            Natural Gasoline                                                              Catalyst:                                                                              0.7% Pd on 30.5% Ni SMM                                              Conditions:                                                                            450°F., 0.5 LHSV, 2.5 H.sub.2 /HC,                                     450 psig                                                             Component        Feed       Product                                                            (wt%)      (wt%)                                             ______________________________________                                        C.sub.1 - C.sub.4           3.6                                               Isopentane       12.1       30.7                                              n-pentane        35.0       15.1                                              2,2-dimethylbutane                                                                             1.9        8.1                                               2,3-dimethylbutane                                                                             3.3        3.9                                               2-methylpentane  16.0       16.6                                              3-methylpentane  11.8       11.8                                              n-hexane         19.9       9.3                                               Estimated RON                                                                  clear of C.sub.5 /C.sub.6                                                     fraction        63         76                                                ______________________________________                                    

Referring to Table VII it can be seen that the C₅ and C₆ components ofthe product are close to their equilibrium concentrations.

HYDROCRACKING

The catalysts of this invention are also useful for the hydrocracking ofhydrocarbons to produce lighter boiling materials than the originalcharge stock. For example, the catalysts of this invention are usefulfor the hydrocracking of aliphatic hydrocarbons to produce lighterboiling materials such as the cracking of raffinates to produce liquidpetroleum gas. The catalysts are also useful for the hydrocracking ofhigher boiling mixtures of hydrocarbons such as those boiling from 450°to 950°F. at atmospheric pressure, especially furnace oils, to producegasoline range hydrocarbons of high octane number. One of the uniquefeatures of the catalysts of this invention is that during thehydrocracking of a furnace oil, the aromatic content of the furnace oilis retained. The ability of the layered clay-type base to retain orpreserve the aromatic content of furnace oils on hydrocracking appearsto be due to the presence of nickel substituted in the lattice. Thecatalysts of this invention are also suitable for the hydrocracking ofhigher boiling stocks such as gas oils or heavier to produce ligherboiling hydrocarbons.

Suitable hydrocracking conditions include a temperature from 350° to1000°F., preferably 500° to 900°F.; a pressure from 250 to 10,000 psig,preferably from 400 to 3000 psig; a liquid hourly space velocity basedon the hydrocarbon charge of 0.1 to 10 volumes of hydrocarbon charge pervolume of catalyst per hour, preferably from 0.25 to 5 v/v/hour; and ahydrogen to hydrocarbon mole ratio of from 0.5:1 to 20:1, preferablyfrom 2:1 to 10:1. The optimum hydrocracking conditions, while generallyfalling within the above ranges, may be varied depending on theparticular charge stock employed. In general, the higher hydrocrackingtemperatures will be employed with the heavier hydrocarbon chargestocks.

It has also been found that the catalysts of this invention are improvedin their hydrocracking ability by a sulfiding treatment. The sulfidingcan be done by any method which is well recognized in the art, such asby the pre-addition of H₂ S in a hydrogen carrier gas to the catalystfor suitable periods of time such as 1 to 24 hours at suitabletemperatures such as 500°F. To 950°F. Sulfiding can also be done duringthe startup procedure by adding sulfur compounds to the charge stock andsulfur can thereafter be added continuously during the run. Suitablesulfur compounds would include H₂ S and carbon disulfide.

The hydrocracking aspect of the invention will be further described withreference to the following experimental work.

NORMAL HEXANE HYDROCRACKING

A series of catalysts were prepared as in Example 4 using nickel acetate(Ni(Ac)₂) as the nickel salt and varying the amount of nickelsubstituted in the lattice. Each of the catalysts was treated to containapproximately 0.5% to 0.7% Pd. The dried catalysts were calcined in airat 1000°F. for 10 hours and then treated with a mixture of 98 percent H₂and 2% H₂ S at 750°F. for 16 hours to sulfide. Normal hexane was passeddownflow through a bed of the catalyst at 650°F., 1.5 liquid hourlyspace velocity based on the n-hexane, 450 psig, and an H₂ /n-hexane moleratio of 2.5. The results of the series of runs are shown in Table VIIIbelow:

                  TABLE VIII                                                      ______________________________________                                        Hydrocracking of N-hexane                                                     Conditions: 1.5 LHSV; 450 psig; 2.5 H.sub.2 /C.sub.6                                                       Weight %                                                                      n-Hexane                                         Example                                                                              Catalyst  Temperature Converted to                                     No.    Wt % Ni   °F.  Cracked Product.sup.a                            ______________________________________                                        28     0.sup.b   650         2                                                29     1.4.sup.c 650         6                                                30     6.8       650         28                                               31     9.7       650         39                                               32     10.1.sup.d                                                                              650         68                                               33     14.3      650         69                                               34     21.6      650         100                                              35     21.6      600         66                                               36     26.4      600         62                                               37     30.5      600         100                                              38     35.7      600         100                                              39     30.5      550         69                                               40     35.7      550         46                                               ______________________________________                                        .sup.a Calculated by dividing weight of cracked                                products recovered by the weight of                                           n-hexane charged.                                                            .sup.b Same as catalyst for Ex. 11 except calcined                             and presulfided as set forth above.                                          .sup.c Same as catalyst for Ex. 1 and then                                     calcined and presulfided as set forth above.                                 .sup.d NiF.sub.2 was salt employed in preparing this                           catalyst.                                                                

EXAMPLE 41

Example 28 was repeated except the catalyst employed was a commerciallyavailable rare-earth exchanged form Linde-type Y molecular sievecontaining 0.5 weight percent palladium. The weight percent hexaneconverted to cracked products was 7.2.

EXAMPLE 42

Example 41 was repeated except the reaction temperature was increased to725°F., which resulted in an increase in hexane converted to crackedproducts to 50 weight percent.

Referring to Table VIII, it can be seen that the substitution of nickelin the lattice of the layered synthetic mica/montmorillonite claygreatly improves the ability of the catalyst to crack normal hexane. Itwould appear that the catalysts of this invention have a temperatureadvantage over other commercial catalysts such as the palladiumcontaining rare-earth exchanged Y-zeolites.

Table IX below shows the complete product distribution for the productsfrom Examples 32, 41 and 42 given above.

Referring to Table IX it can be seen that the nickel-substitutedcatalysts of this invention have a great advantage over the catalystused in Examples 41 and 42. The weight percent isobutane in the product,for example, in Example 32 was 8.7, versus only 1.4 weight percent usingthe Y-zeolite. For example, the catalyst of Example 12 was tested forthe hydrocracking of n-hexane under the conditions of Example 32 above,and only 7 percent of the hexane was converted to cracked productscompared to 68 percent for example 32. This catalyst (15% Ni depositedon SMM) was approximately as active as the Pd-rare earth Y-zeolite ofExample 41 but far less active than the catalyst containing about thesame amount of nickel incorporated into the structure (Ex. 32).

                  TABLE IX                                                        ______________________________________                                        Product Analysis for n-Hexane Hydrocracking                                   Example No.    32        41        42                                         ______________________________________                                        Catalyst       0.7% Pd-  0.5% Pd   0.5% Pd                                                   10% Ni    on rare   on rare                                                             earthy-Y  earth-Y                                                   Sulfided  zeolite   zeolite                                                             sulfided  sulfided                                   Reaction Conditions                                                            Temperature   650°F.                                                                           650°F.                                                                           725°F.                               Pressure, psig                                                                              450       450       450                                         LHSV, v/v/hr  1.5       1.5       1.5                                         H.sub.2 :n-hexane                                                                           2.5       2.5       2.5                                        Product Distribution                                                          (wt % of product)                                                             C.sub.5 +      45.7      95.2      61.2                                       i-C.sub.4       8.7      1.4        6.0                                       n-C.sub.4      10.3      0.4        1.0                                       C.sub.3        33.8      3.0       30.0                                       C.sub.2         1.1      --         1.3                                       C.sub.1         0.4      --         0.5                                       Total C.sub.hd 5 (wt %)                                                                      14.0      2.7       11.7                                       Total C.sub.6 (wt %)                                                                         31.8      92.5      49.5                                       Hexane Converted to                                                           Cracked Products                                                              (wt %)         68.2      7.5       50.5                                       C.sub.6 Distribution                                                           (wt %)                                                                       2,2-dimethylbutane                                                                           11         4        18                                         2,3-dimethylbutane +                                                                         47        42        36                                          2-methylpentane                                                              3-methylpentane                                                                              13        23        21                                         n-hexane       29        31        26                                         ______________________________________                                    

EXAMPLE 43

Example 32 was repeated except the catalyst was prepared using nickelacetate as the salt rather than nickel fluoride. The percent hexaneconversion was 80, while the percent selectivity to C₆ isomers andcracked products was 50 and 50, respectively. The results of this runare also summarized in Table X below.

EXAMPLE 44

Example 43 was repeated except the catalyst additionally contained 2percent fluorine, which was added by the use of HF. The percent hexaneconversion was 89, while the percent selectivity to C₆ isomers andcracked products was 27 and 73 percent, respectively. This run is alsosummarized in Table X below.

EXAMPLE 45

Example 32 was repeated except the catalyst was the same as that used inExample 41. The percent hexane conversion was 72, while the percentselectivity to C₆ isomers and cracking was 90 and 10 percent,respectively. The results of this run are also summarized in Table Xbelow.

                  TABLE X                                                         ______________________________________                                        Hydrocracking.sup.a of n-Hexane                                                                     Wt %                                                                 Wt %     Selectivity.sup.c to                                    Ex.                n-Hexane   C.sub.6                                                                              Cracked                                  No.  Catalyst      Converted.sup.b                                                                          Isomers                                                                              Products                                 ______________________________________                                        32   0.7% Pd-10% Ni.sup.d                                                                        91         25     75                                       43   0.7% Pd-10% Ni.sup.e                                                                        80         50     50                                       44   0.7% Pd-10% Ni.sup.e                                                          plus 2% F by HF                                                                             89         27     73                                       45   0.5% Pd-rare                                                                  earth-Y-Zeolite                                                                             72         90     10                                       ______________________________________                                        .sup.a Hydrocrcking conditions: 650°F.; 450 psig;                       1.5 LHSV; and 2.5 H.sub.2 :n-hexane.                                         .sup.b Conversion calculated by weight of n-hexane                             recovered divided by weight of n-hexane                                       charged.                                                                     .sup.c Selectivity calculated by the weight of                                 products recovered divided by the weight of                                   converted hexane.                                                            .sup.d NiF.sub.2 used as nickel salt.                                         .sup.e Ni(Ac).sub.2 (nickel acetate) used as nickel salt.                 

Referrng to Table X, a comparison of the Examples from this Table andthose in Table VIII shows that the nickel-substituted catalyst made fromnickel fluoride is more active than the catalyst made from nickelacetate. However, the nickel-substituted catalyst using nickel acetateis still more active than the Y-zeolite catalyst. Also, forhydrocracking, the addition of fluorine using HF promotes the activityof the nickel-substituted catalyst made from nickel acetate to about thesame level as the nickel-substituted catalyst which is prepared usingnickel fluoride. This result was unexpected in view of the fact that theaddition of fluorine did not appear to increase the activity of thecatalyst for the isomerization of normal hexane.

EXAMPLE 46

Example 44 was repeated except using a Co substituted catalyst insteadof the nickel substituted catalyst of Example 44. The final catalystcontained about 0.7 % Pd and about 7% Co. The catalyst was prepared in amanner similar to Example 5 above and presulfided for 16 hours at 750°F.using a mixture of 98% H₂ and 2% H₂ S. The weight percent hexaneconverted to cracked products was 5%.

FURNACE OIL HYDROCRACKING

The purpose of the hydrocracking of furnace oil is, in most cases, toproduce a gasoline having as high an octane rating as possible. In someinstances, the main purpose is to produce gaseous olefins such asethylene and propylene. In all instances, the product has a lowerboiling range than the charge stock. The nickel-substituted syntheticmica/montmorillonite catalysts of this invention, especially thosecontaining a hydrogenation component, can suitably be employed in ahydrocracking operation at conventional conditions. Generally, andpreferably, for hydrocracking, a metal or metals having hydrogenationactivity from Groups VI and VIII are incorporated into thenickel-substituted materials of this invention. Any of the metals havinghydrogenation activity as noted above can be employed with the preferredmetals being the noble metals, and especially palladium.

The amount of metals to deposit can be within the ranges set forth abovein the discussion of the catalyst preparation techniques. The method ofadding the metals can also be as set forth above. The catalyst can bedried and calcined as noted above and is preferably presulfided such asby pretreatment at 600°F. and atmospheric pressure using a mixture of 8%H₂ S and 92% hydrogen prior to the furnace oil hydrocracking runs.

Suitable conditions for the hydrocracking of furnace oils are set forthgenerally above under n-hexane hydrocracking. The preferred conditionsfor the hydrocracking of furnace oils include 500 -2500 psig, 0.5-5LHSV, 5000 - 15,000 SCF H₂ /bbl., and 450°-850°F.

While the process of the present invention can be practiced using afurnace oil containing relatively large amounts of nitrogen-containingcompounds, it is preferred to reduce the nitrogen level of the charge toa reasonably low level by prior hydrotreatment before hydrocrackingusing the catalysts of this invention or other suitable hydrogenationcatalysts. For example, it is preferred that the organic nitrogen levelbe less than 10 parts per million (ppm), more preferably less than 1ppm.

FIG. 2 attached is a flow diagram of a preferred scheme for thehydrocracking of a furnace oil to produce a high quality naphtha.

Referring to FIG. 2, the raw furance oil enters through line 10 where itis admixed with fresh hydrogen from line 12 and recycle hydrogen fromline 14 and the admixture is passed downflow through the first reactionzone 16 where it contacts a hydrogenation catalyst under conditionsapplicable for the desulfurization and denitrogenation of the furnaceoil with little hydrocracking. The catalyst can be any of the well knownhydrogenation catalysts such as one or more of the supported Group VI oriron group metals, metal oxides or metal sulfides on a high areasupport, such as an alumina. The catalysts of this invention may also beexployed. The reaction conditions usually include a total pressure of500 to 10,000 psig, preferably 1500 to 3000 psig, and wherein thepartial pressure of hydrogen is 300 to 8000 psig, preferably 1200 to2500 psig. The temperature can suitably be from 400° to 1000°F.,preferably between 500° to 800°F., and the liquid hourly space velocitycan be from 0.1 to 20, preferably from 0.25 to 4 volumes of liquidcharge per volume of catalyst per hour. From 1500 to 10,000, usually3000 to 7000 ft³ of hydrogen are employed per barrel of oil, the flow ofhydrogen being the sum of the fresh hydrogen (line 12); the recyclehydrogen (line 14) and the quench hydrogen (lines 18 and 20).

The pretreated furnace oil exits from reactor 16 through line 22 whereit enters gas separator 24. The function of separator 24 is to removerecycle hydrogen through line 26 for return to reactor 16 through lines14, 18 and 20. The function of the recycle hydrogen entering throughlines 18 and 20 is as a quench to control the temperature in the reactor16.

The remaining products exit from separator 24 through line 28 and enterdistillation zone 30 where fuel gas is removed overhead through line 32.The liquid pretreated furnace oil exits from distillation zone 30through line 34 where it is combined with recycle oil from line 74;fresh hydrogen from line 36; and recycle hydrogen from line 38. Thecombined stream passes downflow through reactor 40 containing a bed ofthe catalyst of this invention. The reaction conditions include a totalpressure of 150 to 10,000 psig, with a hydrogen partial pressure of 100to 8000 psig. The preferred total pressure is 500 to 3000 psig with thepreferred partial pressure of hydrogen as 300 to 2500 psig. Thetemperature can be 400° to 1000°F.; preferably 500° to 800°F. The liquidhourly space velocity can suitably be from 0.1 to 20, preferably 0.5 to5 volumes of liquid charge per volume of catalyst per hour. Quenchhydrogen may enter reactor 40 through lines 42 and 44. The products exitthrough line 46 and enter separator 48 where recycle hydrogen is removedthrough line 50 and enters reactor 40 through lines 38, 42 and 44. Theremaining products exit separator 48 through line 52 and are sent forseparation. For example, the products may enter a distillation zone 54where C₄ and lighter products are removed overhead through line 56 andare further separated in a distillation zone 58 by removal of fuel gasthrough line 60; C₅ hydrocarbons through line 62; and C₄ hydrocarbonsthrough line 64. The bottoms from zone 54 are removed through line 66and enter distillation zone 68 for removal of light gasoline throughline 70; naphtha through 72 and recycle oil through line 74.

The furnace oil hydrocracking aspect of this invention will be furtherdescribed with reference to the following experimental work.

EXAMPLE 47

In the run for this Example, the catalyst was prepared as in Example 1.The catalyst was calcined at 1000°F. for 16 hours and was then sulfidedat 600°F. with a mixture of 8% H₂ S and 92% H₂ for 1 hour. An FCCfurnace oil whose characteristics are given in Table XI below (GR 63903)was passed downflow through a bed of the above catalyst at 700°F., 1500psig, liquid hourly space velocity of 1, together with hydrogen at arate of 10,000 standard cubic feet per barrel. The volume percent yieldof lighter than 400°F. naphtha was 43% by volume. The aromatics contentof the total liquid product was 39 volume percent. Analysis of theliquid products obtained are summarized in Table XII.

                  TABLE XI                                                        ______________________________________                                                        FCC      Pretreated                                                           Furnace  FCC                                                                  Oil      Furnace                                                              GR 63903 Oil                                                                           GR 74103                                             ______________________________________                                        Gravity (ASTM D287-67) °API                                                              23.1       28.6                                             Sulfur (wt %)     0.88       0.0066                                           Nitrogen (ppm)    336        1.0                                              Carbon Residue, Rams                                                           (ASTM D524) wt%  0.10       --                                               Hydrocarbon Type Analysis                                                      FIA (ASTM D1319-70)                                                          Aromatics                                                                              (vol %)      61         58.3                                         Olefins  (vol %)      7          2                                            Saturates                                                                              (vol %)      32         40                                           Distillation (ASTM D86-76)                                                    Overpoint °F.                                                                            386        297                                              Endpoint  °F.                                                                            650        621                                              10%: Volume %     462        440                                              30%               496        470                                              50%               524        496                                              70%               558        525                                              90%               604        570                                              ______________________________________                                    

EXAMPLE 48

Example 47 was repeated except using the catalyst of Example 11 (0.7% Pdon SMM) except the catalyst pretreatment was the same as in Example 47.The yield of lighter than 400°F. naphtha was 56. The results of this runare summarized in Table XII.

                  TABLE XII                                                       ______________________________________                                        Hydrocracking of FCC Furnace Oil (GR 63903)                                   (1500 psig; 700°F.; 1 LVHSV; 10,000 SCF H.sub.2 /Bbl)                                  Ex. 47   Ex. 48                                                               0.7% Pd-Ni                                                                             0.7% Pd-SMM                                                          (i.4%)SMM                                                     ______________________________________                                        On-Stream Time, Hrs.                                                                            4-36       4-36                                             Gravity °API                                                                             43         47.4                                             Sulfur (wt %)     0.05       0.04                                             Nitrogen (ppm)    0.4        3                                                Hydrocarbon Type Analysis                                                     FIA                                                                           Aromatics                                                                              (vol. %)     39         14                                           Olefins  (vol. %)      2          1                                           Saturates                                                                              (vol. %)     59         85                                           Liquid Recovery (vol. %)                                                                         107.3     98                                               <400°F. Naphtha(vol. %)                                                 in Liquid Product                                                                              40         57                                               Vol. % Yield of                                                                <400°F. Naphtha.sup.1                                                                   43         56                                               Vol. % Yield                                                                    of Aromatics.sup.2                                                                            42         14                                               ______________________________________                                        .sup.1 Volume % yield of <400°F. naphtha is cal-                        culated by multiplying Liquid Recovery (%)                                    by Vol. fraction of <400°F. naphtha.                                  .sup.2 Volume % Aromatics is obtained by multiplying                           Liquid Recovery (%) by Vol. fraction of                                       aromatics.                                                               

EXAMPLE 49

The catalyst prepared and pretreated in the same manner as in Example 2above using the pretreatment of Example 47 above was employed.

A pretreated FCC furnace oil (GR 74103) whose characteristics are givenin Table XI above was passed downflow through a bed of the abovecatalyst at 1500 psig, together with hydrogen at at rate of 10,000SCF/bbl., 650°F., and an LHSV of 2. Table XIII shows the hydrocrackingactivity of this catalyst after being lined out.

                  TABLE XIII                                                      ______________________________________                                        Hydrocracking of FCC furnace Oil and                                          Pretreated FCC Furnace Oil                                                    (1500 psig; 650°F.; 10,000 SCF H.sub.2 /bbl)                           with the 0.7% Pd - 10.1% Ni SMM)                                              ______________________________________                                                       Ex. 49     Ex. 50                                                             Pretreated FCC                                                                           Furnace                                                            Furnace Oil                                                                              Oil                                                                (GR 74103) (GR 63903)                                                         2 LHSV     1 LHSV                                              ______________________________________                                        On-Stream Time, Hrs.                                                                           14           16                                              Gravity °API                                                                            81.1         28.9                                            Sulfur (wt %)    0.04         0.31                                            Nitrogen (ppm)   0.6          20.6                                            Hydrocarbon Type Analysis                                                     FIA                                                                           Aromatics                                                                              (vol. %)    2            65                                          Olefins  (vol. %)    0.5          1                                           Saturates                                                                              (vol. %)    97.5         34                                          Liquid Recovery (vol. %)                                                                       52.2         96.2                                            <400°F. Naphtha (vol. %)                                                in Liquid Product                                                                             100          14                                              Volume Yield of                                                                <400°F. Naphtha.sup.a                                                                  52.2         13.47                                           Volume Yield                                                                   of Aromatics.sup.b                                                                            1.04         62.5                                            ______________________________________                                        .sup.2 Calculated by multiplying liquid recovery (%)                           by volume fraction of <400° F. naphtha.                               .sup.b Calculated by multiplying liquid recovery (%)                           by volume fraction of aromatics.                                         

EXAMPLE 50

Example 49 was repeated except the charge stock was the FCC furnace oil(GR 63903) shown in Table XI; the LHSV was 1 and the catalyst was thesame as that used in Example 49 after about 124 hours of operation. Theresults of the run are also summarized in Table XIII above.

Referring to Table XIII, the presence of nitrogen in the feed to Example50 is primarily responsible for the decreased hydrocracking activity ofthe catalyst as shown by the decreased "<400°F. Naphtha (Vol. %) inLiquid Product" and decreased "volume Yield of <400°F. Naphtha".

Comparison runs were made to show the effect of the catalysts of thisinvention on the retention of aromatics using low nitrogen contentfurnace oils. The low nitrogen content furnace oils were obtained byhydrogen pretreatment of FCC furnace oils.

EXAMPLE 51

A pretreated FCC furnace oil whose characteristics are given in Table XIabove was passed downflow through a bed of the same catalyst used inExample 49 at 1500 psig, together with hydrogen at 10,000 SCF H₂ /bbl.,2 LHSV, and a temperature of 600°F. The liquid recovery was 81.1 volumepercent, the volume yield of of <400°F. naphtha was 81.1%, and thevolume of aromatics was 11.0%. More detailed results appear in TableXIV.

EXAMPLE 52

A pretreated FCC furnace oil (GR 74103) whose characteristics are givenin Table XI above was passed downflow through a bed of the same catalystprepared as in Example 11 above except the pretreatment was the same asin Example 47. The reaction conditions included a pressure of 1500 psig;a hydrogen flow rate of 10,000 SCF H₂ /bbl; a 2 LHSV; and a temperatureof 500°F. The liquid recovery was 109 volume %, the volume yield of<400°F. naphtha was 81.8%, and the volume yield of aromatics was 1.1%.More detailed analyses of the product appear in Table XIV.

Comparable conversions were obtained in Examples 51 and 52 as shown bythe similar gravities of the liquid products. As can be seen from TableXIV, the volume yield of aromatics in in the product using the catalystof this invention (Ex. 51) is 11% versus only 1.1% when no nickel issubstituted in the lattice (Ex. 52).

                  TABLE XIV                                                       ______________________________________                                        Hydrocracking of Pretreated FCC Furnace Oil                                   (1500 psig; 2 LVHSV; 10,000 SCF H.sub.2 /Bbl)                                                Ex. 51   Ex. 52                                                               0.7% Pd-Ni                                                                             0.7% Pd-SMM                                                          (10.1%)SMM                                                     ______________________________________                                        On-Stream Time, Hrs.                                                                           8          24                                                Temperature °F.                                                                         600        500                                               Gravity °API                                                                            53.1       51.9                                              Nitrogen (ppm)   0.4        <0.2                                              Hydrocarbon Type Analysis                                                     FIA                                                                           Aromatics                                                                              (vol %)     11.0       1.0                                           Olefins  (vol %)     1.0        0.0                                           Saturates                                                                              (vol %)     88.0       99.0                                          Liquid Recovery (vol %)                                                                        81.1       109                                               <400°F. Naphtha (vol %)                                                 in liquid product                                                                             100        75                                                Volume Yield of                                                               <400°F. Naphtha.sup.1                                                                   81.1       81.8                                              Volume Yield                                                                   of Aromatics.sup.2                                                                            8.9        1.1                                               ______________________________________                                        .sup.1 Calculated by multiplying "Liquid Recovery                              (vol %)" by volume fraction of <400°F.                                 naphtha.                                                                     .sup.2 Calculated by multiplying "Liquid Recovery                              (vol %)" by volume fraction of aromatics.                                

A pretreated FCC furnace oil whose characteristics are given in Table XIabove was used in the following examples to determine the effect of thenickel substitution level on hydrocracking activity and selectivity. Thepretreated FCC furnace oil (GF 74103) was contacted with various nickelsubstituted catalysts under the conditions set forth in Table XV below.The results of the runs are also set forth in Table XV below.

                  TABLE XV                                                        ______________________________________                                        Hydrocracking of Pretreated Furnace Oil                                       (1500 psig; 2 LVHSV; 10,000 SCF H.sub.2 /Bbl)                                                              Liquid                                                                  Gra-  Re-   Aro-  <400°F.                       Ex.  Catalyst.sup.a                                                                          Temp.   vity  covery                                                                              matics                                                                              Naphtha                              No.  Wt % Ni   °F.                                                                            °API                                                                         %     %     %                                    ______________________________________                                        53   0         500     51.9  95     1    75                                   54   1.4       550     56.6  88    13    80                                   55   10        600     53.3  90    17    90                                   56   30.5      565     50    60    25    95                                   ______________________________________                                        .sup.a Catalysts were same as those used in Examples                           11, 6, 8 and 25 respectively, except the                                      pretreatment was the same as Example 47.                                 

Referring to Table XV, the aromatics retention increases with anincreasing nickel content of the catalyst, although at 30.5% nickel (Ex.56), the liquid recovery was down.

A series of runs was made the same as the run for Example 54, except thetemperature was varied. The results are shown in Table XVI below.

                  TABLE XVI                                                       ______________________________________                                                                  Gravity of                                          Example Temp.             Liquid Product                                      No.     °F.        °API                                         ______________________________________                                        57      500               33                                                  54      550               56.6                                                58      600               78                                                  59      650               82                                                  ______________________________________                                    

Similar results were obtained using the catalyst from Example 55.

RAFFINATE HYDROCRACKING

Raffinate for purposes of this application is defined as a predominantlyparaffinic stream which remains after aromatics are extracted from astream containing large amounts of aromatics, such as a reformereffluent. A raffinate having the characteristics shown in Table XVIIbelow was subjected to hydrocracking. Usually a raffinate has a boilingrange from 100°F. to 400°F. at atmospheric pressure (ASTM D-86-76).

                  TABLE XVII                                                      ______________________________________                                        Component              Vol. %                                                 ______________________________________                                        Paraffins              90.80                                                  C.sub.4  0.15                                                                 C.sub.5  2.44                                                                 C.sub.6  71.34                                                                C.sub.7  16.68                                                                C.sub.8 +                                                                              0.19                                                                 Naphthenes             7.11                                                   Aromatics              2.08                                                   ______________________________________                                    

The conditions of hydrocracking and the results are shown in Table XVIIIbelow using a variety of nickel substituted catalysts.

                  TABLE XVIII                                                     ______________________________________                                        Raffinate Hydrocracking                                                       Conditions of Run:                                                                              1000 psig; 2.0 LHSV;                                                          4 H.sub.2 /hydrocarbon.                                     Feed: Raffinate of Table XVII plus                                            1500 ppm S added as CS.sub.2                                                  ______________________________________                                                           Product Yield                                              Ex.  Catalyst.sup.a                                                                          Temp.   C.sub.3 + C.sub.4                                                                     C.sub.5.sup.+                                                                        C.sub.1 + C.sub.2                       No.  Wt % Ni   °F.                                                                            Vol. %  Vol. % Wt %                                    ______________________________________                                        60   0         750     13.5    88.5   0.41                                    61   15        625     48.1    60.0   0.66                                    62   21.6      625     46.3    62.0   0.39                                    63   30.5      600     47.5    60.4   0.8                                     ______________________________________                                        .sup.a Catalysts were the same as those used in Exs.                           11, 21, 23 and 25, respctively, except the                                    catalyst was pretreated for 16 hours at 750°F.                         with a stream of 2% H.sub.2 S - 98% H.sub.2.                             

The desired raffinate product is the volume percent C₃ + C₄ which isdefined here as LPG (liquid petroleum gas). The volume percent LPG isincreased considerably at lower temperatures when using the nickelsubstituted catalysts of this invention. That the catalyst of Example 60was low in activity at 750°F. is shown by the low yield of productshaving three and four carbon atoms.

The catalyst of this invention was also employed for residuedesulfurization. The feedstock was a residue having the characteristicsshown in Table XIX below.

                  TABLE XIX                                                       ______________________________________                                                       Charge    Product                                              Properties     Stock     Example 64                                           ______________________________________                                        Gravity: °API                                                                         15.2      18.4                                                 Sulfur: wt %   4.13      2.32                                                 C.sub.5 Insolubles:                                                           wt %           6.34      4.42                                                 Nickel: ppm    19        14                                                   Vanadium       58        32                                                   ______________________________________                                    

EXAMPLE 64

The charge stock shown in Table XIX above was passed down flow at 1000psig; 700°F.; 5000 SCF of H₂ per barrel of charge and a 1 liquid hourlyspace velocity through a bed of a catalyst consisting of 10% molybdenumdeposited on a layered synthetic mica/montmorillonite containing 10weight percent nickel proxying for the aluminum atoms in the octahedralsites. The 10% nickel substituted material was prepared in a mannersimilar to that described in Example 3 above except no Pd was added. Themolybdenum was deposited from an aqueous solution of ammoniumparamolybdate using the so-called incipient wetness or minimum excesssolution technique. The properties of the product are summarized inTable XIX above.

Referring to Table XIX, it can be seen that almost half the sulfur wasremoved. In contrast, a catalyst consisting of 0.5% Ni, 1% Co and 8%molybdenum deposited on the layered synthetic mica/montmorillonite with0% nickel substitution (the catalyst of Example 11) was substantiallyinactive for residue desulfurization, the product showing 3.9% sulfur.

EXAMPLE 65

26.0 g. of hydrated alumina, Al₂ O₃.3H₂ O (Alcoa C31, 64.9% Al₂ O₃) wereadded with stirring to a polysilicic acid sol which was prepared bypassing sodium silicate over a hydrogen resin. The volume of sol waschosen so as to contain 27.2 g. of SiO₂. 5.0 g. of Co(Ac)₂.4H₂ O, 15.0g. of Ni(Ac)₂.4H₂ O, 0.78 g. of NH₄ F, and 0.42 g. of HF were dissolvedin 75 cc. of water and the solution was added, with stirring, to thesilicaalumina slurry. The pH of the slurry was adjusted to 8.0 usingaqueous ammonia. The final feed slurry was stirred for 30 minutes,charged to a stirred autoclave, heated quickly (1 to 11/2 hrs.) untilthe pressure lined out at 1250 psig (300°C.) and maintained at theseconditions for 4 hours. The product was cooled in the pressure vessel,removed, sheared in a blender to insure homogeneity, filtered and driedat about 250°F. Palladium was added to the dried product usingconventional impregnation techniques. The final catalyst contained 2.5%Co, 7.5% Ni, and 0.5% Pd.

EXAMPLE 66

Example 28 was repeated except using the catalyst of Example 65 and theweight percent n-hexane converted to cracked products was 54%.

Resort may be had to such variations and modifications as fall withinthe spirit of the invention and the scope of the appended claims.

We claim:
 1. A hydrocarbon conversion catalyst comprising:a laminar 2:1layer-lattice aluminosilicate mineral possessing layer-lattice unitcells, each cell having an inherent negative charge balanced by cationsexterior to said unit cell; and a hydrogenation component; said mineralcorresponding to the following overall formula prior to drying andcalcining:

    [(Al.sub.4.sub.-ew.sup.3.sup.+ Y.sub.3w.sup.2.sup.+).sup. VI (Q.sub.8.sub.-x.sup.4.sup.+ Al.sub.x.sup.3.sup.+).sup.IV O.sub.20 (OH).sub.4.sub.-f F.sub.f].sup.. [dC.sup.Y ]

where Al is aluminum; Y is selected from the class consisting of nickel,cobalt and mixtures thereof; Q is at least 0.95 mol fraction siliconions, the remainder consisting of tetravalent ions having an ionicradius not to exceed 0.65 A; and F is fluorine; C is at least onecharge-balancing cation: and where e has a numerical value from 2 to 3inclusive; w has a numerical value from 0.01 to 2 inclusive, with theproviso that the quantity ew have a numerical value from 0.02 to 4inclusive: f has a value of 4 or less; x has a numerical value from 0.05to 2.0 inclusive; y is the valence of the cation C; d is the number ofcations C where the product dy = x + 3 (e-2)w; and wherein said firstbracket represents said layer-lattice unit cell formation and saidsecond bracket represents said charge-balancing cations.
 2. Ahydrocarbon conversion catalyst according to claim 1, wherein thehydrogenation component is at least one of the metals, metal oxides andmetal sulfides from Groups VI and VIII.
 3. A hydrocarbon conversioncatalyst according to claim 2 wherein Q is silicon.
 4. A hydrocarbonconversion catalyst according to claim 3 wherein said C is selected fromthe group consisting of hydrogen, alkaline earth metal, heavy metal,heavy metal partial hydroxy, ammonium, substituted ammonium, andsubstituted phosphonium cations and mixtures thereof.
 5. A catalyst inaccordance with claim 4 wherein C is primarily hydrogen.
 6. Ahydrocarbon conversion catalyst according to claim 5 wherein e has avalue of about 2; w has a value from 0.2 to 1.66; x has a value from 0.5to 2; and the value of f is from 0.5 to 3.75.
 7. A catalyst inaccordance with claim 6 wherein x is about 1.5.
 8. A hydrocarbonconversion catalyst according to claim 7 wherein the hydrogenationcomponent is at least one of the metals, metal oxides and metal sulfidesfrom Group VIII.
 9. A hydrocarbon conversion catalyst according to claim8 wherein the hydrogenation component is palladium.
 10. A hydrocarbonconversion catalyst in accordance with claim 9 wherein the palladium ispresent in a concentration of 0.01 to 5 weight percent of the finalcatalyst.
 11. A hydrocarbon conversion catalyst in accordance with claim10 wherein the palladium is present in the form of a sulfide.